EP0036517A1 - Method of producing highly-shrinkable tows of acrylonitrile polymerisates - Google Patents
Method of producing highly-shrinkable tows of acrylonitrile polymerisates Download PDFInfo
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- EP0036517A1 EP0036517A1 EP81101530A EP81101530A EP0036517A1 EP 0036517 A1 EP0036517 A1 EP 0036517A1 EP 81101530 A EP81101530 A EP 81101530A EP 81101530 A EP81101530 A EP 81101530A EP 0036517 A1 EP0036517 A1 EP 0036517A1
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- EP
- European Patent Office
- Prior art keywords
- carried out
- acrylonitrile
- heating zone
- stretching
- shrinkage
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims description 30
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000010025 steaming Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 description 18
- 238000010411 cooking Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000747 cardiac effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000578 dry spinning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
- D01G1/00—Severing continuous filaments or long fibres, e.g. stapling
- D01G1/06—Converting tows to slivers or yarns, e.g. in direct spinning
- D01G1/08—Converting tows to slivers or yarns, e.g. in direct spinning by stretching or abrading
Definitions
- the invention relates to a method for producing a tear pull by conventional spinning, post-treatment and tearing, the individual fibers of which have a cooking shrinkage of at least 35%.
- Yarns made from such individual fibers are used in numerous article areas, e.g. in the velor or fur imitation range.
- the yarn is produced by spinning individual fibers, which are usually obtained by cutting shrinkable fiber strands.
- Such a method is e.g. described in DE-OS 2 655 172.
- gentle drying must be carried out at temperatures below 60 ° C., which requires an undesirably long time.
- the object of the present invention was therefore the production of high-shrinkage fibers after a more economical drying process at higher temperatures, with higher strength in the shrinking yarn and the possibility of dyeing smaller batches. It has now surprisingly been found that a saturated steam fixation after stretching and before the tearing process gives a cable which meets these requirements. Fulfills.
- the invention therefore relates to a process for the production of high-shrinkage tears from acrylonitrile polymers after conventional spinning, stretching and tearing, characterized in that after stretching and before tearing, saturated steam fixation is not carried out above 140 ° C. and the tearing occurs when the heating zone is warped (HZV). of at least 30% is carried out.
- the steaming time is a maximum of 30 minutes.
- the heating zone of the tearing machine is preferably heated to 120 to 160 ° C.
- a cardiac output of 65% is usually not exceeded when tearing.
- the distortion during tear processing in the heating zone is particularly preferably not less than 30%.
- the tear processing is advantageously carried out at a heating zone temperature of 120 to 150 ° C. and a cardiac output of 40 to 60%.
- Acrylonitrile polymers in the context of the process are polyacrylonitrile or preferably acrylonitrile copolymers with at least 50% by weight of polymerized acrylonitrile.
- Such copolymers contain one or more monomers copolymerizable with acrylonitrile, such as acrylic acid esters, vinyl esters or monomers with dye-affine groups. Dry-spun bundles of threads are preferably used.
- the threads obtained after dry spinning are passed through aqueous baths to extract the residual solvent, being drawn 2 to 6 times, preferably 2 to 3 times.
- the temperature of the aqueous baths is at most 100 ° C., preferably 65 to 75 ° C.
- the stretched threads are dried, as is usual with acrylic cables, by hot air at 140 to 150 ° C after they have been treated with a preparation necessary for further processing.
- the thread bundle is passed through a conventional stuffer box crimp.
- the cable is treated with saturated steam under pressure so that the cable is given the desired shrink height after the tear processing, i.e. the pull.
- a temperature of 140 ° C is not exceeded, since damage can occur at higher temperatures, which is reflected in a deterioration of the raw clay and in a steaming time that is greater than 30 minutes, also in a reduction in the fineness-related maximum tensile force.
- a minimum temperature of 115 ° C in the saturated steam fixing step is required to achieve sufficient cooking shrinkage in the pull.
- the cable can be dyed using a foulard using one of the usual methods, such as pack dyeing or padding of the dye, it having no effect on the shrinking behavior of the pull, whether spinning or e.g. a color of the cable in the bale is selected.
- the dyeing is expediently carried out before the steaming step, because it is known that the dye is fixed by a steaming process.
- the shrinkage that can be achieved in the pull depends on various parameters. It has been found that the higher the comonomer content in the polymer, the lower the stretch ratio when the comonomer content is below 6% by weight, the higher the fixing temperature (saturated steam) and the higher the temperature and the higher the boiling shrinkage HZV are in the tear process.
- the shrinkage force is also important, since the shrinkage has to be triggered against the resistance of the non-shrinking or only slightly shrinking fibers. It has been shown that copolymers with a comonomer content between 6 and 10% by weight can be processed into tears with a higher shrinking force than those with a comonomer content between 2 and 6% by weight.
- the cable While supplying spray steam under 1 bar, the cable was crimped in a stuffer box and placed in a perforated can. After treatment with saturated steam at 120 ° C. in an autoclave, the cable was torn on a tearing machine (type Seydel 671 S) at a heating plate temperature of 120 ° C. and a cardiac output of 58%. The following values were found when testing the individual fibers of the tear cable:
- the fibers of the tear pull showed an average cooking shrinkage of 30%, a maximum cooking shrinkage of m136%, and the yarn spun from this yarn showed a cooking shrinkage of 38.7% with a shrinking force (180 ° C. hot air) of 5.9 mN / tex.
- An acrylonitrile polymer of the same composition as in Example 1 was spun by a conventional dry spinning process.
- the fiber bundle still contained 16.4% by weight of the solvent, which was washed out in a washing-stretching process with the aid of water at an elevated temperature.
- the temperature in the washing tubs was 85 ° C, that in the stretching tubs 95 ° C.
- the speed quotient of the inlet and outlet in the washing-stretching system was 1: 5.0.
- the stretched and washed cable was then given an antistatic finish and was then steamed in a continuous pressure damper (System Tunnel, Serracant, Spain) at 120 ° C., the residence time in the damper being 9.5 minutes.
- the hot, moist cable was dried with hot air from 140 ° C.
- Example 2 The pull obtained was spun into a 250 dtex yarn. The yarn shrinkage was 43.4%.
- the tensile test of the shrunk yarn measured 26.0% elongation and 8.4 cN / tex tensile strength.
- An acrylonitrile copolymer with a composition as described in Examples 1 and 2 was spun dry, in hot water from 85 ° C. to 95 ° C. washed and stretched to 6 times its original length.
- the wet, antistatic cable was curled in a conventional stuffer box and mechanically dewatered to a residual moisture of about 20% by weight. This was followed by dyeing in an aqueous liquor under elevated pressure of 2.1 bar using the known “cable pack” method. After tension-free drying at an air temperature of 140 ° C, the cable was processed into a pull.
- the heating plates were heated to 120 ° C, the HZV was 58%.
- a dry-spun fiber cable made of an acrylonitrile copolymer having the composition 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7% by weight of sodium methallysulfonate is washed in water at 70 ° C. and at the same temperature around 5 times the initial length stretched. The speed after the stretching process is 72 m / min. After applying an antistatic, the product is dried at max. 140 ° C with air, the outlet speed from the dryer is 25% lower than the inlet speed. Before tear processing at 140 ° C Heating plate temperature and a cardiac output of 44%, the 6.84 km long cable stored in a perforated can is treated in an autoclave with saturated steam at 125 ° C.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Artificial Filaments (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Stringed Musical Instruments (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstelllung eines Reißzuges durch übliches Spinnen, Nachbehandeln und Reißen, dessen Einzelfasern einen Kochschrumpf von wenigstens 35 % aufweisen. Garne aus solchen Einzelfasern werden in zahlreichen Artikelgebieten, z.B. im Velour- oder Pelzimitationsbreich, eingesetzt. Die Garnherstellung erfolgt durch Verspinnen von Einzelfasern, die üblicherweise durch Schneiden von schrumpffähigen Fasersträngen erhalten werden. Ein solches Verfahren ist z.B. in der DE-OS 2 655 172 beschrieben. Hierbei muß zur Erhaltung der Schrumpffähigkeit eine schonende Trocknung bei Temperaturen unter 60°C durchgeführt werden, was eine unerwünscht lange Zeit erfordert.The invention relates to a method for producing a tear pull by conventional spinning, post-treatment and tearing, the individual fibers of which have a cooking shrinkage of at least 35%. Yarns made from such individual fibers are used in numerous article areas, e.g. in the velor or fur imitation range. The yarn is produced by spinning individual fibers, which are usually obtained by cutting shrinkable fiber strands. Such a method is e.g. described in DE-OS 2 655 172. In order to maintain the shrinkability, gentle drying must be carried out at temperatures below 60 ° C., which requires an undesirably long time.
Es ist bekannt, daß der erzielbare Faserkochschrumpf vom effektiven Streckgrad abhängt, derart, daß mit höherem Streckgrad dieser Schrumpf im allgemeinen abnimmt. Daraus ergibt sich ein weiterer Nachteil für Hochschrumpffasern: die wegen des niedrigen Streckgrades geringe Festigkeit.It is known that the achievable fiber cooking shrinkage depends on the effective degree of stretching, such that this shrinkage generally decreases with a higher degree of stretching. This results in a further disadvantage for high shrink fibers: the low strength due to the low degree of stretch.
Für verschiedene Einsatzbereiche bei der Artikelherstellung ist es wünschenswert, farbige Garne einzusetzen. Eine Färbung der geschnittenen Einzelfasern oder der Garne kann nicht durchgeführt werden, weil dadurch der vorhandene Schrumpf bereits ausgelöst würde. Hochschrumpffasern müssen deshalb gefärbt werden, bevor sie ihren Schrumpfcharakter erhalten, also üblicherweise in der Spinnmasse. Aus wirtschaftlichen Gründen ist es dabei nicht möglich, bestimmte Partiegrößen mit einer Färbung zu unterschreiten.For different areas of application in the production of articles, it is desirable to use colored yarns. The cut individual fibers or the yarns cannot be dyed because this would already trigger the existing shrinkage. High-shrinkage fibers must therefore be dyed before they get their shrinking character, i.e. usually in the dope. For economic reasons, it is not possible to go below certain batch sizes with a coloring.
Aufgabe der vorliegenden Erfindung war deshalb die Herstellung von hochschrumpfenden Fasern nach einem wirtschaftlicheren Trocknungsprozess bei höheren Temperaturen, mit höherer Festigkeit im Schrumpfgarn und der Möglichkeit, kleinere Chargen zu färben. Es wurde nun überraschenderweise gefunden, daß man durch eine Sattdampffixierung nach der Verstreckung und vor dem Reißprozess ein Kabel erhält, das diese Forderungen. erfüllt.The object of the present invention was therefore the production of high-shrinkage fibers after a more economical drying process at higher temperatures, with higher strength in the shrinking yarn and the possibility of dyeing smaller batches. It has now surprisingly been found that a saturated steam fixation after stretching and before the tearing process gives a cable which meets these requirements. Fulfills.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von hochschrumpfenden Reißzügen aus Acrylnitrilpolymerisaten nach üblichem Spinnen, Strecken und Reißen, dadurch gekennzeichnet, daß nach der Verstreckung und vor dem Reißen eine Sattdampffixierung nicht über 140°C vorgenommen und das Reißen bei einem Heizzonenverzug (HZV) von mindestens 30 % durchgeführt wird. Die Dämpfdauer beträgt maximal 30 Minuten. Die Heizzone der Reißmaschine wird vorzugsweise auf 120 bis 160°C erwärmt.The invention therefore relates to a process for the production of high-shrinkage tears from acrylonitrile polymers after conventional spinning, stretching and tearing, characterized in that after stretching and before tearing, saturated steam fixation is not carried out above 140 ° C. and the tearing occurs when the heating zone is warped (HZV). of at least 30% is carried out. The steaming time is a maximum of 30 minutes. The heating zone of the tearing machine is preferably heated to 120 to 160 ° C.
Üblicherweise wird beim Reißen ein HZV von 65 % nicht überschritten. Besonders bevorzugt beträgt der Verzug bei der Reißverarbeitung in der Heizzone nicht weniger als 30 %. Vorteilhaft erfolgt die Reißverarbeitung bei einer Heizzonentemperatur von 120 bis 150°C und einem HZV von 40 bis 60 %.A cardiac output of 65% is usually not exceeded when tearing. The distortion during tear processing in the heating zone is particularly preferably not less than 30%. The tear processing is advantageously carried out at a heating zone temperature of 120 to 150 ° C. and a cardiac output of 40 to 60%.
Völlig überraschend ist, daß die Trocknung solcher Kabel bei für Hochschrumpffasern außergewöhnlich hohen Temperaturen von 140 bis 150°C ausgeführt werden kann, ohne daß die Schrumpffähigkeit des Reißzugs beeinträchtigt wird. Durch den hohen Verzug bei der Reißverarbeitung erhalten die Einzelfasern und damit die Schrumpfgarne eine ausgezeichnete Festigkeit. Es ist nach dem erfindungsgemäßen Verfahren ohne weiteres möglich, beliebig kleine Chargen nach den bei der Kabelfärbung üblichen Methoden anzufärben, wobei es ohne Einfluß auf das Schrumpfverhalten ist, ob die Färbung vor oder nach dem Dämpfschritt erfolgt, was einen besonderen Vorteil des Verfahrens darstellt.It is completely surprising that the drying of such cables can be carried out at temperatures of 140 to 150 ° C., which are exceptionally high for high-shrink fibers, without the shrinkability of the pull pull being impaired. Due to the high warping during tear processing, the individual fibers and thus the shrink yarns are given excellent strength. According to the method according to the invention, it is readily possible to dye batches of any size using the methods customary in cable dyeing, it having no effect on the shrinkage behavior whether the dyeing takes place before or after the steaming step, which is a particular advantage of the method.
Acrylnitrilpolymerisate im Sinne des Verfahrens sind Polyacrylnitril oder vorzugsweise Acrylnitrilmischpolymerisate mit mindestens 50 Gew.-% an polymerisiertem Acrylnitril. Solche Mischpolymerisate enthalten ein oder mehrere mit Acrylnitril copolymerisierbare Monomere, wie Acrylsäureester, Vinylester oder Monomere mit farbstoffaffinen Gruppen. Vorzugsweise werden trockengesponnene Fadenbündel eingesetzt.Acrylonitrile polymers in the context of the process are polyacrylonitrile or preferably acrylonitrile copolymers with at least 50% by weight of polymerized acrylonitrile. Such copolymers contain one or more monomers copolymerizable with acrylonitrile, such as acrylic acid esters, vinyl esters or monomers with dye-affine groups. Dry-spun bundles of threads are preferably used.
Die nach Trockenspinnen erhaltenen Fäden werden zum Extrahieren des Restlösungsmittels durch wäßrige Bäder geführt, wobei sie auf das 2- bis 6-fache, vorzugsweise auf das 2- bis 3-fache verstreckt werden. Die Temperatur der wäßrigen Bäder beträgt maximal 100°C, vorzugsweise 65 bis 75°C.The threads obtained after dry spinning are passed through aqueous baths to extract the residual solvent, being drawn 2 to 6 times, preferably 2 to 3 times. The temperature of the aqueous baths is at most 100 ° C., preferably 65 to 75 ° C.
Die verstreckten Fäden werden wie bei Acrylkabeln üblich durch heiße Luft von 140 bis 150°C getrocknet, nachdem sie mit einer für die Weiterverarbeitung notwendigen Präparation behandelt wurden. Um den Einzelfäden eine ausreichende Querhaftung zu verleihen, leitet man das Fadenbündel durch eine herkömmliche Stauchkammerkräusel.The stretched threads are dried, as is usual with acrylic cables, by hot air at 140 to 150 ° C after they have been treated with a preparation necessary for further processing. In order to give the individual threads sufficient lateral adhesion, the thread bundle is passed through a conventional stuffer box crimp.
Damit das Kabel nach der Reißverarbeitung, also der Reißzug, die gewünschte Schrumpfhöhe erhält, wird das Kabel mit Sattdampf unter Druck behandelt. Dabei wird eine Temperatur von 140°C nicht überschritten, da bei höheren Temperaturen eine Schädigung eintreten kann, die sich in einer Verschlechterung des Rohtons und bei einer Dämpfdauer, die größer als 30 Minuten ist, auch in einer Verminderung der feinheitsbezogenen Höchstzugkraft zeigt. Andererseits ist zur Erzielung eines ausreichenden Kochschrumpfs im Reißzug eine Mindesttemperatur von 115°C beim Sattdampffixierschritt erforderlich. Besonders vorteilhaft bei dem erfindungsgemäßen Verfahren ist die Austauschbarkeit der Reihenfolge der Verfahrensschritte Präparieren, Kräuseln, Dämpfen, Trocknen. Es ist dem Hersteller überlassen, die für ihn günstigste Kombination zu wählen. So kann bei Einsatz eines Großautoklaven eine ausreichende Menge an Kabel gesammelt werden, um einen wirtschaftlich optimalen Dämpfprozess so durchzuführen, daß das Kabel danach sofort der Reißmaschine vorgelegt werden kann. Ebenso kann eine kontinuierliche Dämpfung in geeigneten Apparaten direkt nach der Verstreckung erfolgen und Avivierung, Kräuselung, Trocknung in beliebiger Reihenfolge anschließend erfolgen.The cable is treated with saturated steam under pressure so that the cable is given the desired shrink height after the tear processing, i.e. the pull. A temperature of 140 ° C is not exceeded, since damage can occur at higher temperatures, which is reflected in a deterioration of the raw clay and in a steaming time that is greater than 30 minutes, also in a reduction in the fineness-related maximum tensile force. On the other hand, a minimum temperature of 115 ° C in the saturated steam fixing step is required to achieve sufficient cooking shrinkage in the pull. The interchangeability of the sequence of the process steps preparation, crimping, steaming, drying is particularly advantageous in the method according to the invention. It is up to the manufacturer to choose the most favorable combination for him. So can when using a large autoclave, a sufficient amount of cable is collected to carry out an economically optimal steaming process so that the cable can then be presented to the tearing machine immediately. Continuous damping in suitable apparatuses can also take place directly after stretching, and finishing, crimping and drying can then take place in any order.
Zur Herstellung eines gefärbten Hochschrumpfreißzuges kann das Kabel nach einer der üblichen Methoden, wie Packfärbung oder Aufklotzen des Farbstoffs mit Hilfe eines Foulards gefärbt werden, wobei es ohne Einfluß auf das Schrumpfverhalten des Reißzugs ist, ob dabei eine Spinngutfärbung oder z.B. eine Färbung des Kabels im Ballen gewählt wird. Zweckmäßigerweise führt man die Färbung jedoch vor dem Dämpfschritt durch, weil bekanntermaßen durch einen Dämpfprozess der Farbstoff fixiert wird.To produce a colored high shrink pull, the cable can be dyed using a foulard using one of the usual methods, such as pack dyeing or padding of the dye, it having no effect on the shrinking behavior of the pull, whether spinning or e.g. a color of the cable in the bale is selected. However, the dyeing is expediently carried out before the steaming step, because it is known that the dye is fixed by a steaming process.
Der im Reißzug erzielbare Kochschrumpf ist von verschiedenen Parametern abhängig. Es wurde gefunden, daß der Kochschrumpf umso höher ist, je höher der Comonomergehalt im Polymerisat ist, je niedriger das Streckverhältnis ist, wenn der Comonomergehalt unter 6 Gew.% liegt, je höher die Fixiertemperatur (Sattdampf) ist und je höher die Temperatur und der HZV beim Reißprozess sind.The shrinkage that can be achieved in the pull depends on various parameters. It has been found that the higher the comonomer content in the polymer, the lower the stretch ratio when the comonomer content is below 6% by weight, the higher the fixing temperature (saturated steam) and the higher the temperature and the higher the boiling shrinkage HZV are in the tear process.
Für bestimmte Artikelbereiche, z.B. bei Pelzimitationen ist neben der Schrumpfhöhe im Reißzug bzw. im Schrumpfgarn auch die Schrumpfkraft von Wichtigkeit, da der Schrumpf gegen den Widerstand der nicht oder nur geringer schrumpfenden Fasern ausgelöst werden muß. Es hat sich gezeigt, daß Copolymerisate mit einem Comonomergehalt zwischen 6 und 10 Gew.-% zu Reißzügen mit höherer Schrumpfkraft verarbeitet werden können, als solche mit einem Comonomergehalt zwischen 2 und 6 Gew.-%.For certain article areas, e.g. in the case of imitations of fur, in addition to the shrinkage height in the pull or in the shrinking yarn, the shrinkage force is also important, since the shrinkage has to be triggered against the resistance of the non-shrinking or only slightly shrinking fibers. It has been shown that copolymers with a comonomer content between 6 and 10% by weight can be processed into tears with a higher shrinking force than those with a comonomer content between 2 and 6% by weight.
Aufgrund der geschilderten Zusammenhänge zwischen Herstellungsparametern und Schrumpfeigenschaften ist es nach dem erfindungsgemäßen Verfahren möglich, Produkte mit gezielten Eingenschaften zu erzeugen.Due to the described relationships between manufacturing parameters and shrink properties, it is possible according to the method according to the invention to produce products with specific properties.
Ein Acrylnitrilcopolymerisat auf 90,48 Gew.-% Acrylnitril, 9,0 Gew.-% Acrylsäuremethylester und 0,52 Gew.-% Natriummethallylsulfonat wurde nach dem üblichen Trockenspinnverfahren gesponnen. Das Spinnkabel mit einer Gesamtstärke von ca. 230 g/m wurde in einer Wasch-Streck-Anlage bei 85°C in Wasser gewaschen und in zwei Stufen bei einer Temperatur von 95°C 1 : 6,0 verstreckt. Nach Aufbringen einer antistatischen Avivage ließ man das Kabel in einem mit Dampf von 102°C beschickten Rohr um 29 % schrumpfen und anschließend unter Spannung mit Luft von 135°C auf eine Feuchte von 1,2 Gew.-% trocknen. Unter Zuführung von Sprühdampf unter 1 bar wurde das Kabel in einer Stauchkammer gekräuselt und in eine perforierte Kanne abgelegt. Nach einer Behandlung mit Sattdampf von 120°C in einem Autoklaven wurde das Kabel auf einer Reißmaschine (Typ Seydel 671 S) bei 120°C Heizplattentemperatur und einem HZV von 58 % gerissen. Bei der Prüfung der Einzelfasern des Reißkabels wurden folgende Werte gefunden:
Die Fasern des Reißzuges zeigten einen mittleren Kochschrumpf von 30 %, einen maximalen Kochschrumpf von m136 %, das aus diesen ersponnene Garn einen Kochschrumpf von 38,7 % bei einer Schrumpfkraft (180°C Heißluft) von 5,9 mN/tex.The fibers of the tear pull showed an average cooking shrinkage of 30%, a maximum cooking shrinkage of m136%, and the yarn spun from this yarn showed a cooking shrinkage of 38.7% with a shrinking force (180 ° C. hot air) of 5.9 mN / tex.
Ein Acrylnitrilpolymerisat gleicher Zusammensetzung wie in Beispiel 1 wurde nach üblichem Trockenspinnverfahren versponnen. Das Faserbündel enthielt noch 16,4 Gew.-% des Lösungsmittels, welches in einem Wasch-Streck-Verfahren mit Hilfe von Wasser bei erhöhter Tempertaur ausgewaschen wurde. Die Temperatur in den Waschwannen betrug 85°C, die in den Streckwannen 95°C. Der Geschwindigkeitsquotient von Ein- und Auslauf in der Wasch-Streck-Anlage betrug 1 : 5,0. Danach erhielt das gestreckte und gewaschene Kabel eine antistatische Avivage und wurde anschließend in einem kontinuierlichen Druckdämpfer (System Tunnel, Fa. Serracant, Spanien) bei 120°C gedämpft, wobei die Verweilzeit im Dämpfer 9,5 Minuten betrug. Das heiße, feuchte Kabel wurde mit Heißluft von 140°C bis auf eine Restfeuchte von 0,9 Gew.-% getrocknet, gekräuselt und auf der in Beispiel 1 genannten Reißmaschine bei 160°C 50 % zwischen den Heizplatten gedehnt. Der erhaltene Reißzug wurde zu einem Garn vom Titer 250 dtex versponnen. Der Kochschrumpf des Garns lag bei 43,4 %. Bei der Reißprüfung des ausgeschrumpften Garns wurden 26,0 % Dehnung und 8,4 cN/tex Reißkraft gemessen.An acrylonitrile polymer of the same composition as in Example 1 was spun by a conventional dry spinning process. The fiber bundle still contained 16.4% by weight of the solvent, which was washed out in a washing-stretching process with the aid of water at an elevated temperature. The temperature in the washing tubs was 85 ° C, that in the stretching tubs 95 ° C. The speed quotient of the inlet and outlet in the washing-stretching system was 1: 5.0. The stretched and washed cable was then given an antistatic finish and was then steamed in a continuous pressure damper (System Tunnel, Serracant, Spain) at 120 ° C., the residence time in the damper being 9.5 minutes. The hot, moist cable was dried with hot air from 140 ° C. to a residual moisture content of 0.9% by weight, crimped and stretched 50% between the heating plates at 160 ° C. on the tearing machine mentioned in Example 1. The pull obtained was spun into a 250 dtex yarn. The yarn shrinkage was 43.4%. The tensile test of the shrunk yarn measured 26.0% elongation and 8.4 cN / tex tensile strength.
Ein Acrylnitrilcopolymerisat mit einer wie in den Beispielen 1 und 2 beschriebenen Zusammensetzung wurde trocken versponnen, in heißem Wasser von 85°C - 95°C gewaschen und dabei auf das 6-fache seiner ursprünglichen Länge verstreckt. Das nasse, mit einem Antistatikum versehene Kabel wurde in einer üblichen Stauchkammer gerkäuselt und dabei bis auf eine Restfeuchte von ca. 20 Gew.-% mechanisch entwässert. Anschließend erfolgte eine Färbung in wäßriger Flotte unter erhöhtem Druck von 2,1 bar nach dem bekannten "Kabelpack"-Verfahren. Nach einer spannungslosen Trocknung bei einer Lufttemperatur von 140°C wurde das Kabel zu Reißzug verarbeitet. Die Heizplatten waren auf 120°C erwärmt, der HZV betrug 58 %. Der Reißzug schrumpfte um 41 %, das daraus hergestellte Garn um 43,4 %.An acrylonitrile copolymer with a composition as described in Examples 1 and 2 was spun dry, in hot water from 85 ° C. to 95 ° C. washed and stretched to 6 times its original length. The wet, antistatic cable was curled in a conventional stuffer box and mechanically dewatered to a residual moisture of about 20% by weight. This was followed by dyeing in an aqueous liquor under elevated pressure of 2.1 bar using the known “cable pack” method. After tension-free drying at an air temperature of 140 ° C, the cable was processed into a pull. The heating plates were heated to 120 ° C, the HZV was 58%. The tear pull shrank by 41%, the yarn made from it by 43.4%.
Ein trockengesponnenes Faserkabel aus einem Acrylnitrilcopolymerisat der Zusammensetzung 93,6 Gew.-% Acrylnitril, 5,7 Gew.-% Acrylsäuremethylester und 0,7 Gew.-% Natriummethallysulfonat wird in Wasser bei 70°C gewaschen und bei gleicher Temperatur um das 2,5-fache der Ausgangslänge verstreckt. Die Geschwindigkeit nach dem Streckprozess beträgt 72 m/min. Nach Auftragen eines Antistatikums trocknet man das Produkt bei max. 140°C mit Luft, wobei die Auslaufgeschwindigkeit aus dem Trockner um 25 % geringer ist als die Einlaufgeschwindigkeit. Vor der Reißverarbeitung bei 140°C Heizplattentemperatur und einem HZV von 44 % wird das in einer perforierten Kanne abgelegte Kabel von 6,84 km Länge in einem Autoklaven mit Sattdampf von 125°C behandelt. Dabei werden 5 Dampfstöße von je 2 min Dauer und 7 Evakuierphasen von je 2 min Dauer durchgeführt, um eine gleichmäßige Erwärmung der Einzelfasern zu gewährleisten. Die Einzelfasern des Reißzuges haben einen Kochschrumpf zwischen 32 und 39 %, wobei das Maximum der Verteilungskurve bei 36 % liegt. Nach der Ausspinnung eines Garns (250 dtex) aus diesem Reißzug wird ein Garnkochschrumpf von 43 % gemessen.A dry-spun fiber cable made of an acrylonitrile copolymer having the composition 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7% by weight of sodium methallysulfonate is washed in water at 70 ° C. and at the same temperature around 5 times the initial length stretched. The speed after the stretching process is 72 m / min. After applying an antistatic, the product is dried at max. 140 ° C with air, the outlet speed from the dryer is 25% lower than the inlet speed. Before tear processing at 140 ° C Heating plate temperature and a cardiac output of 44%, the 6.84 km long cable stored in a perforated can is treated in an autoclave with saturated steam at 125 ° C. 5 bursts of steam, each lasting 2 minutes, and 7 evacuation phases, each lasting 2 minutes, are carried out in order to ensure uniform heating of the individual fibers. The individual fibers of the pull have a boiling shrinkage between 32 and 39%, the maximum of the distribution curve being 36%. After spinning a yarn (250 dtex) from this pull, a yarn boil shrinkage of 43% is measured.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81101530T ATE5334T1 (en) | 1980-03-15 | 1981-03-04 | PROCESS FOR THE MANUFACTURE OF HIGH SHRINKABLE TEARS FROM ACRYLIC NITRILE POLYMERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3010045 | 1980-03-15 | ||
| DE19803010045 DE3010045A1 (en) | 1980-03-15 | 1980-03-15 | METHOD FOR THE PRODUCTION OF HIGH-SHRINKABLE ZIPPERS FROM ACRYLNITRILE POLYMERISATION |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0036517A1 true EP0036517A1 (en) | 1981-09-30 |
| EP0036517B1 EP0036517B1 (en) | 1983-11-16 |
Family
ID=6097341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81101530A Expired EP0036517B1 (en) | 1980-03-15 | 1981-03-04 | Method of producing highly-shrinkable tows of acrylonitrile polymerisates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4434530A (en) |
| EP (1) | EP0036517B1 (en) |
| JP (1) | JPS56144215A (en) |
| AT (1) | ATE5334T1 (en) |
| CA (1) | CA1156413A (en) |
| DE (2) | DE3010045A1 (en) |
| ES (1) | ES500335A0 (en) |
| IE (1) | IE50868B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2596072A1 (en) * | 1986-03-24 | 1987-09-25 | Italiana Brodotti Acrilici Spa | METHOD OF CONTINUOUSLY RETRIEVING A THERMALLY THERMALLY TAPERABLE FIBER RIBBON |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3225268A1 (en) * | 1982-07-06 | 1984-01-12 | Bayer Ag, 5090 Leverkusen | CONTINUOUS DRY SPINNING PROCESS FOR HIGH-SHRINKABLE ACRYLNITRILE THREADS AND FIBERS |
| JP2552455Y2 (en) * | 1991-06-18 | 1997-10-29 | 旭化成工業株式会社 | towel |
| US6352948B1 (en) | 1995-06-07 | 2002-03-05 | Kimberly-Clark Worldwide, Inc. | Fine fiber composite web laminates |
| US5972499A (en) * | 1997-06-04 | 1999-10-26 | Sterling Chemicals International, Inc. | Antistatic fibers and methods for making the same |
| US7100246B1 (en) * | 1999-06-14 | 2006-09-05 | E. I. Du Pont De Nemours And Company | Stretch break method and product |
| US20060204753A1 (en) * | 2001-11-21 | 2006-09-14 | Glen Simmonds | Stretch Break Method and Product |
| US7581376B2 (en) * | 2004-02-27 | 2009-09-01 | E.I. Du Pont De Nemours And Company | Spun yarn, and method and apparatus for the manufacture thereof |
| CN101146938A (en) * | 2005-01-21 | 2008-03-19 | 纳幕尔杜邦公司 | Staple yarn manufacturing process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1435338A1 (en) * | 1963-11-21 | 1970-02-12 | Asahi Chemical Ind | Process for the production of thread yarn |
| UST884016I4 (en) * | 1970-06-29 | 1971-03-16 | Defensive publication | |
| US3852948A (en) * | 1961-08-26 | 1974-12-10 | J Ruddell | Yarns, tows, and fibers having differential shrinkability |
| JPS5037298B1 (en) * | 1970-05-09 | 1975-12-01 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3052512A (en) | 1960-06-14 | 1962-09-04 | American Cyanamid Co | Art of producing polyacrylonitrile filamentary materials |
| US3177555A (en) | 1960-08-09 | 1965-04-13 | Eastman Kodak Co | Process for treating textile filaments |
| US3503100A (en) | 1966-09-08 | 1970-03-31 | Eastman Kodak Co | Method of processing large denier tow |
| DE2420472A1 (en) | 1974-04-27 | 1975-11-13 | Bayer Ag | METHOD OF MANUFACTURING LUXURY YARN |
| US4011294A (en) | 1974-06-18 | 1977-03-08 | E. I. Du Pont De Nemours And Company | Process for making high shrinkage acrylic fibers |
| DE2454322A1 (en) | 1974-11-15 | 1976-05-20 | Bayer Ag | Dry-spun nodacrylic fibres - from acrylonitrile vinyl chloride and chlorine and sulphur contg copolymers |
| DE2502195C2 (en) | 1975-01-21 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | Process for the production of acrylic fibers or threads |
| US4071596A (en) | 1975-06-20 | 1978-01-31 | E. I. Du Pont De Nemours And Company | Process for making high shrinkage acrylic fibers |
| DE2622920A1 (en) | 1976-05-21 | 1977-12-01 | Bayer Ag | CROSS-LINKED ACRYLONITRILE COPOLYMERISATES |
| DE2655172A1 (en) | 1976-12-06 | 1978-06-08 | Du Pont | High-shrinkage acrylic fibre prodn. - by wash drawing at critical bath temp. cooling and drying under specified conditions |
| DE2658916A1 (en) | 1976-12-24 | 1978-07-06 | Bayer Ag | POLYACRYLNITRILE FILAMENT YARN |
-
1980
- 1980-03-15 DE DE19803010045 patent/DE3010045A1/en not_active Ceased
-
1981
- 1981-03-04 DE DE8181101530T patent/DE3161396D1/en not_active Expired
- 1981-03-04 EP EP81101530A patent/EP0036517B1/en not_active Expired
- 1981-03-04 AT AT81101530T patent/ATE5334T1/en not_active IP Right Cessation
- 1981-03-05 US US06/241,199 patent/US4434530A/en not_active Expired - Fee Related
- 1981-03-13 ES ES500335A patent/ES500335A0/en active Granted
- 1981-03-13 IE IE555/81A patent/IE50868B1/en unknown
- 1981-03-13 CA CA000373000A patent/CA1156413A/en not_active Expired
- 1981-03-13 JP JP3547581A patent/JPS56144215A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852948A (en) * | 1961-08-26 | 1974-12-10 | J Ruddell | Yarns, tows, and fibers having differential shrinkability |
| DE1435338A1 (en) * | 1963-11-21 | 1970-02-12 | Asahi Chemical Ind | Process for the production of thread yarn |
| JPS5037298B1 (en) * | 1970-05-09 | 1975-12-01 | ||
| UST884016I4 (en) * | 1970-06-29 | 1971-03-16 | Defensive publication |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2596072A1 (en) * | 1986-03-24 | 1987-09-25 | Italiana Brodotti Acrilici Spa | METHOD OF CONTINUOUSLY RETRIEVING A THERMALLY THERMALLY TAPERABLE FIBER RIBBON |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56144215A (en) | 1981-11-10 |
| ES8201650A1 (en) | 1981-12-16 |
| IE50868B1 (en) | 1986-08-06 |
| DE3161396D1 (en) | 1983-12-22 |
| EP0036517B1 (en) | 1983-11-16 |
| IE810555L (en) | 1981-09-15 |
| DE3010045A1 (en) | 1981-09-24 |
| ES500335A0 (en) | 1981-12-16 |
| US4434530A (en) | 1984-03-06 |
| CA1156413A (en) | 1983-11-08 |
| ATE5334T1 (en) | 1983-12-15 |
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